Alloy compositions and techniques for reducing intermetallic compound thickness and oxidation of metals and alloys

ABSTRACT

Alloy compositions and techniques for reducing IMC thickness and oxidation of metals and alloys are disclosed. In one particular exemplary embodiment, the alloy compositions may be realized as a composition of alloy or mixture consisting essentially of from about 90% to about 99.999% by weight indium and from about 0.001% to about 10% by weight germanium and unavoidable impurities. In another particular exemplary embodiment, the alloy compositions may be realized as a composition of alloy consisting essentially of from about 90% to about 99.999% by weight gallium and from about 0.001% to about 10% by weight germanium and unavoidable impurities.

CROSS-REFERENCE TO RELATED APPLICATIONS

This patent application claims priority to U.S. Provisional PatentApplication No. 60/746,710, filed May 8, 2006, which is herebyincorporated by reference herein in its entirety.

FIELD OF THE DISCLOSURE

The present disclosure relates generally to electrical and thermalconduction and, more particularly, alloy compositions and techniques forreducing intermetallic compound (IMC) thickness and oxidation of metalsand alloys.

BACKGROUND OF THE DISCLOSURE

When working with electronic devices, solder joints should givesufficient reliability during service. Solder joint reliability largelyrelies on IMC growth that is caused by time and heat generated duringservice. In general, thicker IMC causes reliability problems due tobrittleness of IMC, formation of Kirkendall voiding, and/or depletion ofmetal layer(s) upon which solder is applied, especially, when the metallayer(s) is thin such as in under bump metallization (UBM).

On the other hand, the development of new thermal interface materials(TIM's) is required to address increases in device processing speeds andheat generation. Thermal solders are very attractive because they havehigh thermal conductivities. Soldered TIM's have similar problems assolder joints in that IMC growth causing reliability problems may occuras devices run at elevated temperatures.

Low melting point metals, including liquid metals, are also useful asthermally conductive materials due to good conformity of the low meltingpoint metals with contacting surfaces, good metallic phase continuity ofthe low melting point metals at service temperatures, and the formationof good thermally conductive pathways or chains of the low melting pointmetals at service temperatures. The use of low melting point metals,however, is limited in some specific applications due to rapid oxidationand high reactivity.

New types of TIM's, such as polymer solder hybrids (PSH), have beenrecently introduced wherein a polymer matrix acts as an adhesive on asurface of a die or package and solder filler serves as a thermalconductor. Several possible applications of low melting point metalshave been attempted as thermal conductive fillers or as a part ofconductive fillers in PSH's. However, low melting point metals,including liquid metals, oxidize very quickly and form looselyaggregated solids, which easily delaminate at interfaces. As a result,using this type of TIM is very challenging.

In view of the foregoing, it would be desirable to provide techniquesfor reducing IMC thickness and oxidation of metals and alloys whichovercome the above-described inadequacies and shortcomings.

SUMMARY OF THE DISCLOSURE

Alloy compositions and techniques for reducing IMC thickness andoxidation of metals and alloys are disclosed. In one particularexemplary embodiment, the alloy compositions may be realized as acomposition of alloy or mixture consisting essentially of from about 90%to about 99.999% by weight indium and from about 0.001% to about 10% byweight germanium and unavoidable impurities. In another particularexemplary embodiment, the alloy compositions may be realized as acomposition of alloy or mixture consisting essentially of from about 90%to about 99.999% by weight indium and from about 0.001% to about 10% byweight of one or more of germanium, manganese, phosphorus, and titanium.In yet another particular exemplary embodiment, the alloy compositionsmay be realized as a composition of alloy consisting essentially of fromabout 90% to about 99.999% by weight gallium and from about 0.001% toabout 10% by weight germanium and unavoidable impurities. In stillanother particular exemplary embodiment, the alloy compositions may berealized as a composition of alloy consisting essentially of from about90% to about 99.999% by weight gallium and from about 0.001% to about10% by weight of one or more of germanium, manganese, phosphorus, andtitanium. In still yet another particular exemplary embodiment, thealloy compositions may be realized as a composition of alloy consistingessentially of gallium-indium alloy, gallium-indium-tin alloy,gallium-indium-tin-zinc alloy, cadmium, cadmium alloys, indium-leadalloy, indium-lead-silver alloy, mercury, mercury alloys, bismuth-tinalloy, indium-tin-bismuth alloy, and mixtures thereof containing fromabout 0.001% to about 10% by weight of one or more of germanium,manganese, phosphorus, and titanium and unavoidable impurities.

The alloy compositions may take the form of a metallurgical interconnectmaterial, a thermal interface material, a thermally conductive filler,or a thermally conductive medium. The thermal interface material maycomprise one or more of a phase change material, a thermally conductivegel, a thermally conductive tape, and a thermal grease.

In one particular exemplary embodiment, the techniques may be realizedas a method of incorporating from about 0.001% to about 10% by weight ofone or more dopants including one or more of germanium, manganese,phosphorus, and titanium in a metal or metal alloy comprising from about90% to about 99.999% by weight gallium or indium, wherein the methodcomprises mixing the one or more dopants into the metal or metal alloyas a solution with heat. The mixture may be quickly cooled to get finerdopant or intermetallic particles that diffuse faster than largerparticles.

In another particular exemplary embodiment, the techniques may berealized as a method of incorporating from about 0.001% to about 10% byweight of one or more dopants including one or more of germanium,manganese, phosphorus, and titanium in a metal or metal alloy comprisingfrom about 90% to about 99.999% by weight gallium or indium, wherein themethod comprises mixing the one or more dopants as particulates into amolten metal or metal alloy, and cooling the molten metal or metal alloywith the one or more dopant particulates to form a metal or metal alloycomposite.

In another particular exemplary embodiment, the techniques may berealized as a method of incorporating from about 0.001% to about 10% byweight of one or more dopants including one or more of germanium,manganese, phosphorus, and titanium in a metal or metal alloy comprisingfrom about 90% to about 99.999% by weight gallium or indium, wherein themethod comprises mixing the one or more dopants into a solid form of themetal or metal alloy by mechanical force.

In another particular exemplary embodiment, the techniques may berealized as a method of incorporating from about 0.001% to about 10% byweight of one or more dopants including one or more of germanium,manganese, phosphorus, and titanium in a metal or metal alloy comprisingfrom about 90% to about 99.999% by weight gallium or indium, wherein themethod comprises mixing the one or more dopants as particulates into ametal or metal alloy powder to form a metal or metal alloy powdermixture.

In another particular exemplary embodiment, the techniques may berealized as a method of incorporating from about 0.001% to about 10% byweight of one or more dopants including one or more of germanium,manganese, phosphorus, and titanium in a metal or metal alloy comprisingfrom about 90% to about 99.999% by weight gallium or indium, wherein themethod comprises putting the one or more dopants as particulates in aninterconnecting substrate with the metal or metal alloy, wherein theinterconnecting substrate may include at least one of a pad on circuitboard, a heat spreader, a heat sink, and a back side of component.

The present disclosure will now be described in more detail withreference to exemplary embodiments thereof as shown in the accompanyingdrawings. While the present disclosure is described below with referenceto exemplary embodiments, it should be understood that the presentdisclosure is not limited thereto. Those of ordinary skill in the arthaving access to the teachings herein will recognize additionalimplementations, modifications, and embodiments, as well as other fieldsof use, which are within the scope of the present disclosure asdescribed herein, and with respect to which the present disclosure maybe of significant utility.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to facilitate a fuller understanding of the present disclosure,reference is now made to the accompanying drawings, in which likeelements are referenced with like numerals. These drawings should not beconstrued as limiting the present disclosure, but are intended to beexemplary only.

FIG. 1 is a table of IMC thickness and Nickel (Ni) layer consumption ofaged pure Indium (In) and 2% Germanium (Ge)/Indium (In) samples inaccordance with an embodiment of the present disclosure.

FIG. 2 shows a scanning electron microscopy (SEM) picture, magnified×1000, of a pure Indium (In) sample on a Nickel (Ni)/Gold (Au) substrateaged for 1000 hrs at 150° C. in accordance with an embodiment of thepresent disclosure.

FIG. 3 shows a scanning electron microscopy (SEM) picture, magnified×1000, of a 2% Germanium (Ge)/Indium (In) sample on a Nickel (Ni)/Gold(Au) substrate aged for 1000 hrs at 150° C. in accordance with anembodiment of the present disclosure.

FIG. 4 shows a scanning electron microscopy (SEM) picture, magnified×3000, of a 2% Germanium (Ge)/Indium (In) sample on a Nickel (Ni)/Gold(Au) substrate aged for 1000 hrs at 150° C. in accordance with anembodiment of the present disclosure.

FIG. 5 is a table of IMC compositions of aged pure Indium (In) and 2%Germanium (Ge)/Indium (In) samples in accordance with an embodiment ofthe present disclosure.

FIG. 6 shows a graph of oxide formed in a 85° C./85% relative humiditychamber for pure Gallium (Ga) and 0.05% and 0.1% Germanium (Ge)-dopedGallium (Ga) in accordance with an embodiment of the present disclosure.

FIG. 7 shows a graph of oxide formed in a 85° C./85% relative humiditychamber for 0.5%, 1%, 2%, and 5% Germanium (Ge)-doped Gallium (Ga) inaccordance with an embodiment of the present disclosure.

FIG. 8 shows a graph of oxide formed in a 85° C./85% relative humiditychamber for 0.0001% and 0.0005% Germanium (Ge)-doped Gallium (Ga) inaccordance with an embodiment of the present disclosure.

FIG. 9 shows a graph of oxide formed in a 85° C./85% relative humiditychamber for Gallium (Ga)/Indium (In) alloys with and without 0.5%Germanium (Ge) in accordance with an embodiment of the presentdisclosure.

FIG. 10 shows a graph of oxide formed in a 85° C./85% relative humiditychamber for Indium (In)/Bismuth (Bi) alloys with and without 0.5%Germanium (Ge) in accordance with an embodiment of the presentdisclosure.

FIG. 11 shows a graph of oxide formed in a 85° C./85% relative humiditychamber for Gallium (Ga) alloys containing 0.5% Phosphorus (P), 0.5%Titanium (Ti), 0.5% Manganese (Mn), and no dopants in accordance with anembodiment of the present disclosure.

FIG. 12 is a table of relative peak intensity of Germanium (Ge) toGallium (Ga) with different laser power for 2% Germanium (Ge)/Gallium(Ga) in accordance with an embodiment of the present disclosure.

FIG. 13 shows a graph of ICP-MS spectrum of 2% Germanium (Ge)/Gallium(Ga) for 15% laser power in accordance with an embodiment of the presentdisclosure.

FIG. 14 shows a graph of ICP-MS spectrum of 2% Germanium (Ge)/Gallium(Ga) for 25% laser power in accordance with an embodiment of the presentdisclosure.

FIG. 15 shows a mounting configuration wherein a metallurgical bond isformed between a pad of an electronic component and a pad of a substratethrough an interconnecting material, such as solder, in accordance withan embodiment of the present disclosure.

FIG. 16 shows an application of a TIM in an electronic assembly inaccordance with an embodiment of the present disclosure.

FIG. 17 shows a simplified example of a first TIM in the form of a phasechange material, a thermally conductive gel, a thermally conductivetape, or a thermal grease that comprises a polymeric matrix filled witha thermally conductive filler between an IHS and an electronic componentin accordance with an embodiment of the present disclosure.

FIG. 18 shows an example wherein a first TIM is a PSH where a thermallyconductive filler stays as a liquid at service temperature and apolymeric matrix gives mechanical adhesion between an IHS and anelectronic component in accordance with an embodiment of the presentdisclosure.

FIG. 19 shows an example wherein TIM material may be placed directlybetween an IHS and an electronic component without a polymeric matrix inaccordance with an embodiment of the present disclosure.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

Alloy compositions and techniques for reducing IMC thickness andoxidation of metals and alloys in accordance with embodiments of thepresent disclosure are described. Such alloy compositions and techniqueswere discovered through experimental testing. For example, in order tosolve problems of solder joint reliability, an IMC growth test was usedto reveal a technique for preventing IMC growth of interconnect materialsuch as solder and TIM in accordance with an embodiment of the presentdisclosure. That is, significant, unprecedented effects were observedwhen IMC growths of 2% (wt) Germanium (Ge)/Indium (In) and pure Indium(In) on an electrolytic Nickel (Ni)/Gold (Au) substrate after aging in a150° C. oven for 1000 hours. IMC thickness and Nickel (Ni) layerconsumption of samples were measured after aging the samples. As shownin the table of FIG. 1, total IMC thickness of pure Indium (In) wasabout 18.8-19.6 microns while the IMC thickness of 2% Germanium(Ge)/Indium (In) was about 2.0-3.4 microns. The original thickness ofNickel (Ni) layer of the substrate was 5.3 microns and the Nickel (Ni)layer consumption of samples with pure Indium (In) and 2% Germanium(Ge)/Indium (In) were determined as 45.3-49.1% and 3.8-7.5%,respectively. FIGS. 2 and 3 show scanning electron microscopy (SEM)pictures of a pure Indium (In) sample and a 2% Germanium (Ge)/Indium(In) sample, respectively, on an electrolytic Nickel (Ni)/Gold (Au)substrate after aging in a 150° C. oven for 1000 hours. The decrease inIMC in the 2% Germanium (Ge)/Indium (In) sample is readily apparent.When seen at higher magnification, it is also apparent that the IMCconsists of three layers (see FIG. 4).

In order to understand the mechanism for thinner IMC in germanium-dopedindium, energy dispersive spectrometry (EDS) is helpful and thus wasperformed. The table of FIG. 5 summarizes EDS analysis results for thepure Indium (In) sample and the 2% Germanium (Ge)/Indium (In) sample.

Summarizing, as shown in FIG. 2, only one layer of IMC is found in thepure Indium (In) sample. However, as shown in FIGS. 3 and 4, threelayers of IMC are found in the 2% Germanium (Ge)/Indium (In) sample. Asshown in the table of FIG. 5, the composition of the IMC in the pureIndium (In) sample was determined to be (Ni, Au)₂₈In₇₂, Meanwhile, thecomposition of the first IMC layer (i.e., closest to solder) of the 2%Germanium (Ge)/Indium (In) sample was determined to be 54% Indium (In),32% Nickel (Ni), 13% Germanium (Ge), and 1% Gold (Au). It should benoted, however, that the actual composition of the first IMC layer ofthe 2% Germanium (Ge)/Indium (In) sample may not be precisely accuratebecause the first IMC layer of the 2% Germanium (Ge)/Indium (In) samplewas thinner than the measurement resolution. Thus, materials in areasother than the first IMC layer of the 2% Germanium (Ge)/Indium (In)sample may be included in the composition of the first IMC layer of the2% Germanium (Ge)/Indium (In) sample. The second IMC layer of the 2%Germanium (Ge)/Indium (In) sample, however, was thicker than the firstIMC layer of the 2% Germanium (Ge)/Indium (In) sample and thus it waspossible to determine the exact composition of the second IMC layer ofthe 2% Germanium (Ge)/Indium (In) sample as (Ni, In, Au)₅₀Ge₅₀. Thecomposition of third IMC layer of the 2% Germanium (Ge)/Indium (In)sample was same as the composition of the IMC in the pure Indium (In)sample.

It is believed that Germanium (Ge) reacts with Nickel (Ni) in the earlystages of aging to form Germanium (Ge)-rich IMC layers and that theseGermanium (Ge)-rich IMC layers protect the Nickel (Ni) layer fromreaction with solder. It is also believed that when a certain IMC layerforms a dense and stable layer that can block inter-diffusion betweensolder and a substrate material, thinner total IMC and less consumptionof the substrate material such as for UBM is observed. Thus, it isfurther believed that formation of such a protective IMC layer resultsin better reliability. From the discussion above, it may be concludedthat the thin layer(s) of Germanium (Ge)-rich IMC plays a role asdiffusion barrier to slow down solder diffusion to substrate.

In order to solve problems of oxidation of metals, including low meltingtemperature metals, an oxidation test was used to reveal a technique forpreventing oxidation in accordance with an embodiment of the presentdisclosure. Indeed, the above-described significant, unprecedentedeffects of Germanium (Ge) were also observed in low melting temperaturemetals such as gallium in the oxidation test. That is, samples of lowmelting temperature metals 99.95% Gallium (Ga)/0.05% Germanium (Ge),99.9% Gallium (Ga)/0.1% Germanium (Ge), and pure Gallium (Ga) wereplaced in a 85° C./85% relative humidity chamber. Metal oxide formed ontop of the metals in a vial. The amount of oxide was determined bymeasuring the height of the oxide part (volume) formed on top of themetals. The amount of oxide for the pure Gallium (Ga) sample increasedrapidly and showed about 90% oxide in 10 days. In contrast, the samplesof Gallium (Ga) containing small amounts of Germanium (Ge) showed muchslower oxidation rates. Indeed, the 99.95% Gallium (Ga)/0.05% Germanium(Ge) and 99.9% Gallium (Ga)/0.1% Germanium (Ge) samples didn't show asignificant amount of oxide until after 80 days in the 85° C./85%relative humidity chamber (see FIG. 6).

To see if higher concentrations of Germanium (Ge) may give betteroxidation properties, samples of Gallium (Ga) containing 0.5, 1, 2, and5% (wt) Germanium (Ge) were tested. As shown in FIG. 7, there is no bigimprovement by using higher concentrations of Germanium (Ge).

To check for a lower limit of the effective amount of Germanium (Ge),0.0001% Germanium (Ge)/Gallium (Ga) and 0.0005% Germanium (Ge)/Gallium(Ga) were tested. As shown in FIG. 8, only a slight effect was observedfor these alloys.

Gallium (Ga)/Indium (In) is a eutectic alloy and thus may also be a goodthermal interface material. The anti-oxidation effect of Germanium (Ge)on such an alloy would therefore be of interest in view of the abovefindings. Therefore, the oxidation rate of a 78.6% Gallium (Ga)/21.4%Indium (In) alloy was compared with a 0.5% Germanium (Ge)/78.2% Gallium(Ga)/21.3% Indium (In) alloy. As shown in FIG. 9, the Germanium(Ge)-containing Gallium (Ga)/Indium (In) alloy showed a much more stableoxidation property.

Bismuth (Bi)/Indium (In) is also a eutectic alloy and thus may also be agood thermal interface material. The anti-oxidation effect of Germanium(Ge) on such an alloy would therefore be of interest in view of theabove findings. Therefore, the oxidation rate of a 66.7% Indium(In)/33.3% Bismuth (Bi) alloy was compared with a 0.5% Germanium(Ge)/66.4% Indium (In)/33.1% Bismuth (Bi) alloy. As shown in FIG. 10,only a slight anti-oxidation effect was observed for the Germanium(Ge)-containing Indium (In)/Bismuth (Bi) alloy.

For comparison purposes, the anti-oxidation effect of other dopants onGallium (Ga) would be of interest in view of the above findings.Therefore, the oxidation rate of 0.5% Phosphorus (P)/Gallium (Ga), 0.5%Titanium (Ti)/Gallium (Ga), and 0.5% Manganese (Mn)/Gallium (Ga) werecompared with pure Gallium (Ga). As shown in FIG. 11, someanti-oxidation effect was observed for the Phosphorus (P), Titanium(Ti), and Manganese (Mn)-doped Gallium (Ga), but not as much asGermanium (Ge)-doped Gallium (Ga).

The mechanism for using Germanium (Ge) to protect Gallium (Ga) fromoxidation was investigated. It was assumed that a thin Germanium(Ge)-containing protective layer was formed and that this layerprotected further reaction of Gallium (Ga) with oxygen. A laser ablationICP-MS method was used to verify this mechanism. The laser ablationICP-MS method is widely used for surface composition analysis. Duringthis method a high energy laser ablates a small area of the surface of asample. The ablated material is then transferred into an ICP-MS analysischamber. The higher the laser intensity, the deeper the ablation.

When lower laser power (15%) was used so that the ablation was shallow,the relative intensity of the Germanium (Ge) major peak (68.8-68.9) was31-32% to the Gallium (Ga) major peak (68.8-68.9) for 2% Germanium(Ge)/Gallium (Ga). When the higher laser power (25%) was used, therelative intensity of Germanium (Ge) was 8-10%. The results givequalitative evidence that the Germanium (Ge) atoms go to the surface toprotect the alloy from oxidation. The test has repeated at a differentspot of the sample and showed the same result. FIGS. 12-14 show theanalysis results.

Referring to FIG. 15, there is shown a mounting configuration wherein ametallurgical bond is formed between a pad 2 of an electronic component1 and a pad 4 of a substrate 5 through an interconnecting material 3,such as solder, in accordance with an embodiment of the presentdisclosure. IMC layers build up between the solder interconnectingmaterial 3 and the component pad 2 and/or the substrate pad 4. Thecompositions described herein may reduce IMC growth between the solderinterconnecting material 3 and the component pad 2 and/or the substratepad 4 to increase reliability of the electronic component 1.

Referring to FIG. 16, there is shown an application of a TIM in anelectronic assembly in accordance with an embodiment of the presentdisclosure. The electronic assembly comprises a substrate 5 connected toan electronic component 1 through interconnecting material 10. Anintegrated heat spreader (IHS) 8 is attached to a top side of theelectronic component 1 using a first TIM 9 to dissipate heat generatedfrom the electronic component 1. The IHS 8 is also connected to a heatsink 6 by a second TIM 7 for further dissipation of heat.

One of the most effective materials for the first TIM 9 and the secondTIM 7 is a thermal solder such as indium, indium alloys, gallium-indiumalloy, gallium-indium-tin alloy, gallium-indium-tin-zinc alloy,indium-lead alloy, indium-lead-silver alloy, bismuth-tin alloy, andindium-tin-bismuth alloy. The compositions described herein may reduceIMC growth between the electronic component 1 and the IHS 8 and/orbetween the IHS 8 and the heat sink 6 to increase reliability.

Referring to FIG. 17, there is shown a simplified example of the firstTIM 9 in the form of a phase change material, a thermally conductivegel, a thermally conductive tape, or a thermal grease that comprises apolymeric matrix 12 filled with a thermally conductive filler 11 betweenthe IHS 8 and the electronic component 1 in accordance with anembodiment of the present disclosure. The conductive filler 11 mayinclude indium, indium alloys, gallium, gallium-indium alloy,gallium-indium-tin alloy, gallium-indium-tin-zinc alloy, cadmium,cadmium alloys, indium-lead alloy, indium-lead-silver alloy, mercury,mercury alloys, bismuth-tin alloy, and indium-tin-bismuth alloy. Thecompositions described herein may improve oxidation properties andreduce reactivity of the thermally conductive filler 11.

Referring to FIG. 18, there is shown an example wherein the first TIM 9is a PSH where a thermally conductive filler 13 stays as a liquid atservice temperature and the polymeric matrix 12 gives mechanicaladhesion between the IHS 8 and the electronic component 1 in accordancewith an embodiment of the present disclosure. The thermally conductivefiller 13 may include indium, gallium, gallium-indium alloy,gallium-indium-tin alloy, gallium-indium-tin-zinc alloy, cadmium,cadmium alloys, indium-lead alloy, indium-lead-silver alloy, mercury,mercury alloys, bismuth-tin alloy, and indium-tin-bismuth alloy. Thecompositions described herein may improve oxidation properties andreduce reactivity of the thermally conductive filler 13.

Referring to FIG. 19, there is shown an example wherein TIM material 15may be placed directly between the IHS 8 and the electronic component 1without the polymeric matrix 12 in accordance with an embodiment of thepresent disclosure. The TIM material 15 may be liquid metal such asgallium or low melting point metals or alloys. A confiner 14 may be usedto prevent the TIM material 15 in liquid form from leaking out frombetween the IHS 8 and the electronic component 1. The compositionsdescribed herein may improve oxidation properties and reduce reactivityof the TIM material 15.

The present disclosure is not to be limited in scope by the specificembodiments described herein. Indeed, other various embodiments of andmodifications to the present disclosure, in addition to those describedherein, will be apparent to those of ordinary skill in the art from theforegoing description and accompanying drawings. Thus, such otherembodiments and modifications are intended to fall within the scope ofthe present disclosure. Further, although the present disclosure hasbeen described herein in the context of a particular implementation in aparticular environment for a particular purpose, those of ordinary skillin the art will recognize that its usefulness is not limited thereto andthat the present disclosure may be beneficially implemented in anynumber of environments for any number of purposes. Accordingly, theclaims set forth below should be construed in view of the full breadthand spirit of the present disclosure as described herein.

1. A composition of alloy or mixture consisting essentially of fromabout 90% to about 99.999% by weight indium and from about 0.001% toabout 10% by weight germanium and unavoidable impurities.
 2. Acomposition of alloy or mixture consisting essentially of from about 90%to about 99.999% by weight indium and from about 0.001% to about 10% byweight of one or more of germanium, manganese, phosphorus, and titanium.3. A composition of alloy consisting essentially of from about 90% toabout 99.999% by weight gallium and from about 0.001% to about 10% byweight germanium and unavoidable impurities.
 4. A composition of alloyconsisting essentially of from about 90% to about 99.999% by weightgallium and from about 0.001% to about 10% by weight of one or more ofgermanium, manganese, phosphorus, and titanium.
 5. A composition ofalloy consisting essentially of gallium-indium alloy, gallium-indium-tinalloy, gallium-indium-tin-zinc alloy, cadmium, cadmium alloys,indium-lead alloy, indium-lead-silver alloy, mercury, mercury alloys,bismuth-tin alloy, indium-tin-bismuth alloy, and mixtures thereofcontaining from about 0.001% to about 10% by weight of one or more ofgermanium, manganese, phosphorus, and titanium and unavoidableimpurities.
 6. A method of incorporating from about 0.001% to about 10%by weight of one or more dopants including one or more of germanium,manganese, phosphorus, and titanium in a metal or metal alloy comprisingfrom about 90% to about 99.999% by weight gallium or indium, the methodcomprising: mixing the one or more dopants into the metal or metal alloyas a solution with heat.
 7. The method of claim 6, further comprising:cooling the mixture quickly to get finer dopant or intermetallicparticles that diffuse faster than larger particles.
 8. A method ofincorporating from about 0.001% to about 10% by weight of one or moredopants including one or more of germanium, manganese, phosphorus, andtitanium in a metal or metal alloy comprising from about 90% to about99.999% by weight gallium or indium, the method comprising: mixing theone or more dopants as particulates into a molten metal or metal alloy;and cooling the molten metal or metal alloy with the one or more dopantparticulates to form a metal or metal alloy composite.
 9. A method ofincorporating from about 0.001% to about 10% by weight of one or moredopants including one or more of germanium, manganese, phosphorus, andtitanium in a metal or metal alloy comprising from about 90% to about99.999% by weight gallium or indium, the method comprising: mixing theone or more dopants into a solid form of the metal or metal alloy bymechanical force.
 10. A method of incorporating from about 0.001% toabout 10% by weight of one or more dopants including one or more ofgermanium, manganese, phosphorus, and titanium in a metal or metal alloycomprising from about 90% to about 99.999% by weight gallium or indium,the method comprising: mixing the one or more dopants as particulatesinto a metal or metal alloy powder to form a metal or metal alloy powdermixture.
 11. A method of incorporating from about 0.001% to about 10% byweight of one or more dopants including one or more of germanium,manganese, phosphorus, and titanium in a metal or metal alloy comprisingfrom about 90% to about 99.999% by weight gallium or indium, the methodcomprising: putting the one or more dopants as particulates in aninterconnecting substrate with the metal or metal alloy.
 12. The methodof claim 11, wherein the interconnecting substrate includes at least oneof a pad on circuit board, a heat spreader, a heat sink, and a back sideof component.
 13. A metallurgical interconnect material formed of thecomposition in any of claims 1 to
 5. 14. A thermal interface materialformed of the composition in any of claims 1 to
 5. 15. The thermalinterface material of claim 14, further comprising one or more of aphase change material, a thermally conductive gel, a thermallyconductive tape, and a thermal grease.
 16. A thermally conductive fillerformed of the composition in any of claims 1 to
 5. 17. A thermallyconductive medium formed of the composition in any of claims 1 to 5.